CN115066413A - Triamide compounds and compositions comprising the same - Google Patents
Triamide compounds and compositions comprising the same Download PDFInfo
- Publication number
- CN115066413A CN115066413A CN202080095909.3A CN202080095909A CN115066413A CN 115066413 A CN115066413 A CN 115066413A CN 202080095909 A CN202080095909 A CN 202080095909A CN 115066413 A CN115066413 A CN 115066413A
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- Prior art keywords
- tert
- compound
- bis
- benzamide
- cis
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- 239000002991 molded plastic Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The triamide compounds have the structure (I) of formula (I)
Wherein R is 1 、R 2 And R 3 Independently selected from alkyl groups. The polymer composition comprises a triamide compound of formula (I) and a polyolefin polymer. The polymer composition comprising the triamide compound of formula (I) exhibits very low haze waterAnd minimal leaching of the triamide compound.
Description
Technical Field
The present application relates to triamide compounds (in particular, triamide derivatives formally derived from 3, 5-diaminobenzoic acid) and compositions comprising the same.
Background
Polymer resins are widely used in various fields, particularly because they have excellent processability, mechanical properties (particularly on a relative weight basis), electrical properties, and the like. While the polymers themselves may have beneficial properties, additives may be used to further enhance those properties and/or mitigate the disadvantages.
Polyolefins are a particularly versatile group of polymer resins. Polyolefins are semi-crystalline polymers. Polyolefins that have been allowed to cool relatively slowly (e.g., cooling that occurs during the production of molded plastic parts) comprise amorphous regions in which the polymer chains are randomly arranged and crystalline regions in which the polymer chains have adopted an ordered configuration. Within these crystalline regions of the polyolefin, the polymer chains are arranged into domains commonly referred to as "crystalline lamellae". Under normal processing conditions, as the polyolefin polymer cools from the molten state, crystalline lamellae grow radially in all directions. This radial growth results in the formation of spherulites, which are spherical semi-crystalline regions consisting of multiple crystalline lamellae interrupted by amorphous regions. The size of the spherulites is influenced by several parameters, and their diameter can vary from hundreds of nanometers to millimeters. When the size of the spherulites is significantly larger than the wavelength of visible light, the spherulites will scatter the visible light passing through the polymer. This scattering of visible light results in a hazy appearance commonly referred to as "polymer haze" or simply "haze". While significant levels of polymer haze may be acceptable in some applications, in certain applications (e.g., storage containers), consumers desire relatively clear plastics, which require correspondingly low haze levels.
Several methods have been developed over the years to reduce haze in polyolefins. One approach that has achieved great commercial success has been the use of clarifying agents. Clarifying agents are additives (typically organic compounds) that, when melt processed with a polymer, can nucleate the crystallization of the cooled polymer and reduce the spherulite size or even substantially prevent the formation of these effective light scattering entities. For example, bis (3, 4-dimethylbenzylidene) sorbitol has enjoyed great commercial success due to its ability to reduce haze in polypropylene polymers. However, bis (3, 4-dimethylbenzylidene) sorbitol is not without its limitations. In particular, clarifying agents cannot reduce haze in polypropylene polymers to a point comparable to the haze levels of more clear polymers (e.g., polystyrene and acrylic). The residual haze of polymers clarified with bis (3, 4-dimethylbenzylidene) sorbitol limits their applications and end uses.
Other clarifying agents have been developed in an attempt to solve the limiting problem of sorbitol acetals (e.g., bis (3, 4-dimethylbenzylidene) sorbitol). For example, triamide compounds (e.g., triamide derivatives formally derived from 1,3, 5-benzenetriamine, 3, 5-diaminobenzoic acid, 5-aminoisophthalic acid, or trimesic acid) initially show promise because relatively low loadings of such compounds can produce haze levels in polypropylene polymers that are comparable to those obtained with bis (3, 4-dimethylbenzylidene) sorbitol. Despite their initial promise, the disclosed triamide compounds still do not produce haze levels comparable to those of more clear polymers. Furthermore, many of the disclosed triamide compounds may leach (extract) from the polypropylene to which they are added. These undesirable levels of leaching make these triamide compounds less suitable for use in food contact and medical applications (i.e., applications in which a polymer clarified with a triamide compound is in contact with food [ e.g., food storage or packaging ] or in a medical device [ e.g., syringe ]), where industry preferences and/or regulations require that the additive exhibit minimal leaching from the polymer.
Thus, there remains a need for clarifying agents that are capable of both producing the desired low haze levels in polyolefin polymers and also exhibit minimal leaching from the polyolefin polymers to which they are added. There remains a need for polymer compositions that incorporate such clarifying agents and exhibit the desired combination of low haze and minimal clarifying agent leaching. Various embodiments described herein seek to provide such fining agents and compositions.
Disclosure of Invention
In a first embodiment, the present invention provides a compound of formula (I)
(I)
Wherein R is 1 、R 2 And R 3 Independently selected from alkyl groups.
In a second embodiment, the present invention provides a polymer composition comprising a compound of formula (I) and a polyolefin polymer.
Detailed Description
In a first embodiment, the present invention provides a compound of formula (I) below, which is a triamide derivative formally derived from 3, 5-diaminobenzoic acid. The structure of formula (I) is as follows:
(I)
in the formula (I), the radical R 1 、R 2 And R 3 Independently selected from alkyl groups.
Radical R 1 、R 2 And R 3 Any suitable alkyl group may be used. In a preferred embodiment, R 1 、R 2 And R 3 Independently selected from C 1 -C 20 Alkyl (e.g. C) 3 -C 20 Alkyl), more preferably C 1 -C 12 Alkyl (e.g. C) 3 -C 12 Alkyl) even more preferably C 1 -C 8 Alkyl (e.g. C) 3 -C 8 Alkyl) and most preferably C 1 -C 5 Alkyl (e.g. C) 2 -C 5 Alkyl or C 3 -C 5 Alkyl). Suitable alkyl groups may be either linear or branched. In a preferred embodiment, R 1 、R 2 And R 3 At least one of which is a branched alkyl group. If R is 1 、R 2 And R 3 Only one of them being a branched alkyl radical, R 2 Or R 3 Branched alkyl groups are preferred. Or, in which R 1 、R 2 And R 3 In another embodiment where only one of is a branched alkyl group, R 1 Branched alkyl groups are preferred. In another preferred embodiment, R 1 、R 2 And R 3 At least two of which are independently selected branched alkyl groups. In such an embodiment, R 2 And R 3 Preferably independently selected branched alkyl groups. In yet another preferred embodiment, R 1 、R 2 And R 3 Each of which is an independently selected branched alkyl group. In those embodiments comprising branched alkyl groups, the alkyl group may comprise any suitable number of carbon atoms, with a preferred example being C 3 -C 20 Branched alkyl, C 3 -C 12 Branched alkyl, C 3 -C 8 Branched alkyl and C 3 -C 5 A branched alkyl group. Suitable branched alkyl groups preferably contain a branch point located at the alpha-carbon or beta-carbon relative to the cyclohexanediyl moiety.
In a preferred embodiment, R 1 、R 2 And R 3 Independently selected from the group consisting of n-propyl, isopropyl, n-butyl, sec-butyl (i.e., butan-2-yl or 1-methylpropyl), isobutyl (i.e., 2-methylpropyl), tert-butyl (i.e., 1, 1-dimethylethyl), n-pentyl, tert-pentyl (i.e., 2-methylbutan-2-yl or 1, 1-dimethylpropyl), neopentyl (i.e., 2, 2-dimethylpropyl), isopentyl (i.e., 3-methylbutyl), sec-pentyl (i.e., pentan-2-yl or 1-methylbutyl), sec-isopentyl (i.e., 3-methylbutan-2-yl or 1, 2-dimethylpropyl), pentan-3-yl (i.e., 1-ethylpropyl) and 2-methylbutyl. In a more preferred embodiment, R 1 、R 2 And R 3 Independently selected from the group consisting of n-propyl, isopropyl, n-butyl, sec-butyl (i.e., butan-2-yl or 1-methylpropyl), isobutyl (i.e., 2-methylpropyl), tert-butyl (i.e., 1, 1-dimethylethyl), tert-pentyl (i.e., 2-methylbutan-2-yl or 1, 1-dimethylpropyl), sec-pentyl (i.e., pentan-2-yl or 1-methylbutyl), sec-isopentyl (i.e., 3-methylbutan-2-yl or 1, 2-dimethylpropyl), and pentan-3-yl (i.e., 1-ethylpropyl). In yet another preferred embodiment, R 1 、R 2 And R 3 Independently selected from the group consisting of n-propyl, isopropyl, n-butyl, isobutyl (i.e., 2-methylpropyl), tert-butyl (i.e., 1, 1-dimethylethyl) and tert-pentyl (i.e., 2-methylbut-2-yl or 1, 1-dimethylpropyl).
As mentioned above, R 1 、R 2 And R 3 At least one of them is preferably a branched alkyl group. Thus, in a preferred embodiment, R 1 、R 2 And R 3 At least one of which is selected from the group consisting of isopropyl, sec-butyl (i.e., butan-2-yl or 1-methylpropyl), isobutyl (i.e., 2-methylpropyl), tert-butyl (i.e., 1, 1-dimethylethyl), tert-pentyl (i.e., 2-methylbutan-2-yl or 1, 1-dimethylpropyl), neopentyl (i.e., 2, 2-dimethylpropyl), isopentyl (i.e., 3-methylbutyl), sec-pentyl (i.e., pentan-2-yl or 1-methylbutyl), sec-isopentyl (i.e., 3-methylbutan-2-yl or 1, 2-dimethylpropyl), pentan-3-yl (i.e., 1-ethylpropyl), and 2-methylbutyl. In another preferred embodiment, R 1 、R 2 And R 3 At least one of which is selected from isopropyl, sec-butyl (i.e., butan-2-yl or 1-methylpropyl), isobutyl(i.e., 2-methylpropyl), tert-butyl (i.e., 1, 1-dimethylethyl), tert-pentyl (i.e., 2-methylbut-2-yl or 1, 1-dimethylpropyl), sec-pentyl (i.e., pent-2-yl or 1-methylbutyl), sec-isopentyl (i.e., 3-methylbut-2-yl or 1, 2-dimethylpropyl), and pent-3-yl (i.e., 1-ethylpropyl). In a more preferred embodiment, R 1 、R 2 And R 3 At least one of which is selected from isopropyl, isobutyl (i.e., 2-methylpropyl), tert-butyl (i.e., 1, 1-dimethylethyl) and tert-pentyl (i.e., 2-methylbut-2-yl or 1, 1-dimethylpropyl). In yet another preferred embodiment, R 1 、R 2 And R 3 At least one of which is selected from the group consisting of tert-butyl (i.e., 1, 1-dimethylethyl) and tert-pentyl (i.e., 2-methylbut-2-yl or 1, 1-dimethylpropyl). In a preferred embodiment, R 2 Or R 3 Is a branched alkyl group independently selected from one of the groups listed in this paragraph. In another preferred embodiment, R 2 And R 3 Each branched alkyl group independently selected from one of the groups listed in this paragraph. Finally, in another preferred embodiment, R 1 、R 2 And R 3 Each of which is a branched alkyl group independently selected from one of the groups listed in this paragraph.
In a preferred embodiment, the compound is selected from
(i) N- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-isopropylcyclohexylcarbonylamino ] -benzamide;
(ii) n- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iii) n- (4-N-propylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iv) n- (4-N-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(v) n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-isopropylcyclohexylcarbonylamino ] -benzamide;
(vi) n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(vii) n- (4-tert-amylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(viii) n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide; and
(ix) n- (4-tert-amylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide; and
(x) Mixtures thereof (i.e., mixtures of two or more of any of the foregoing compounds).
In another preferred embodiment, the compound is selected from
(i) N- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(ii) n- (4-N-propylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iii) n- (4-N-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iv) n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(v) n- (4-tert-pentylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(vi) n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide;
(vii) n- (4-tert-amylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide; and
(viii) mixtures thereof (i.e., mixtures of two or more of any of the foregoing compounds).
In a preferred embodiment, the compound of formula (I) is N- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-isopropylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (4-N-propylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (4-N-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-isopropylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (4-tert-pentylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (4-tert-pentylcyclohexyl) -3, 5-bis- [ 4-tert-pentylcyclohexylcarbonylamino ] -benzamide.
As can be seen in formula (I), each cyclohexanediyl moiety is substituted with a non-hydrogen substituent (i.e., R) at both the 1-and 4-positions 1 、R 2 Or R 3 Groups and amide substituted benzene moieties). The non-hydrogen substituents attached to each cyclohexanediyl moiety may be arranged in two different spatial arrangements relative to each other. The two non-hydrogen substituents may be located on the same side of the mean plane (mean plane) of the cyclohexane ring, which corresponds to the cis configuration; or two non-hydrogen substituents may be located on opposite sides of the average surface of the cyclohexane ring, which corresponds to the trans configuration. R 1 、R 2 And R 3 Each of the groups may be disposed in either the cis or trans position relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In a preferred embodiment, R 1 、R 2 And R 3 At least one of the groups is disposed in a cis position relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In another preferred embodiment, R 1 、R 2 And R 3 At least two of the groups are disposed in cis position relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In yet another preferred embodiment, R 1 、R 2 And R 3 Each of the groups being arranged oppositelyIn the cis position of the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety.
In a preferred embodiment, the compound is selected from
(i) N- (cis-4-isopropylcyclohexyl) -3, 5-bis- [ cis-4-isopropylcyclohexylcarbonylamino ] -benzamide;
(ii) n- (cis-4-isopropylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iii) n- (cis-4-N-propylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iv) n- (cis-4-N-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(v) n- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-isopropylcyclohexylcarbonylamino ] -benzamide;
(vi) n- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(vii) n- (cis-4-tert-amylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(viii) n- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-amylcyclohexylcarbonylamino ] -benzamide; and
(ix) n- (cis-4-tert-amylcyclohexyl) -3, 5-bis- [ cis-4-tert-amylcyclohexylcarbonylamino ] -benzamide; and
(x) Mixtures thereof (i.e., mixtures of two or more of any of the foregoing compounds).
In another preferred embodiment, the compound is selected from
(i) N- (cis-4-isopropylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(ii) n- (cis-4-N-propylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iii) n- (cis-4-N-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(iv) n- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(v) n- (cis-4-tert-pentylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide;
(vi) n- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-amylcyclohexylcarbonylamino ] -benzamide;
(vii) n- (cis-4-tert-amylcyclohexyl) -3, 5-bis- [ cis-4-tert-amylcyclohexylcarbonylamino ] -benzamide; and
(viii) mixtures thereof (i.e., mixtures of two or more of any of the foregoing compounds).
In a preferred embodiment, the compound of formula (I) is N- (cis-4-isopropylcyclohexyl) -3, 5-bis- [ cis-4-isopropylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (cis-4-isopropylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (cis-4-N-propylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (cis-4-N-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-isopropylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (cis-4-tert-amylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide. In another preferred embodiment, the compound of formula (I) is N- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-pentylcyclohexylcarbonylamino ] -benzamide. In yet another preferred embodiment, the compound of formula (I) is N- (cis-4-tert-amylcyclohexyl) -3, 5-bis- [ cis-4-tert-amylcyclohexylcarbonylamino ] -benzamide.
The present application also includes compositions comprising one or more compounds of formula (I), for example, compositions comprising a mixture of two or more compounds of formula (I). (in this case, the cis-isomer and the trans-isomer are considered to be different compounds, such that a mixture of two or more isomers constitutes a composition comprising a mixture of two or more compounds of formula (I)). In such embodiments, it is preferred that 60% or more of the R in all compounds of formula (I) present in the composition is 1 、R 2 And R 3 The groups are located in cis relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. More preferably, about 65% or more of R in all compounds of formula (I) present in the composition 1 、R 2 And R 3 The groups are located in cis relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In another preferred embodiment, about 70% or more of the R in all compounds of formula (I) present in the composition 1 、R 2 And R 3 The groups are located in cis relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In yet another preferred embodiment, about 75% or more of the R in all compounds of formula (I) present in the composition 1 、R 2 And R 3 The groups are located in cis relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In another preferred embodiment, about 80% or more of the R in all compounds of formula (I) present in the composition 1 、R 2 And R 3 The groups are located in cis relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In yet another preferred embodiment, about 85% or more of the R in all compounds of formula (I) present in the composition 1 、R 2 And R 3 The groups are located in cis relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety. In another preferred embodiment, about 90% or more of the R of all compounds of formula (I) present in the composition 1 、R 2 And R 3 The groups being situated opposite to the link to the corresponding cyclohexaneCis-position of the non-hydrogen substituent at the 1-position of the diyl moiety. In yet another preferred embodiment, about 95% or more (e.g., about 96% or more, about 97% or more, about 98% or more, or about 99% or more) of the R in all compounds of formula (I) present in the composition 1 、R 2 And R 3 The groups are located in cis relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety.
In another preferred embodiment of the composition comprising a mixture of two or more compounds of formula (I), about 60 mole% or more of the compounds of formula (I) present in the composition have R's each positioned cis to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group. More preferably, about 65 mole% or more of the R's in the compound of formula (I) present in the composition each having a cis position relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group. In yet another preferred embodiment, about 70 mole% or more of the R's in the compounds of formula (I) present in the composition each having a cis position relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group. In another preferred embodiment, about 75 mole% or more of the R's in the compound of formula (I) present in the composition each having a cis position relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group. In yet another preferred embodiment, about 80 mole% or more of the compounds of formula (I) present in the composition have R's each positioned cis to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group. In another preferred embodiment, about 85 mole% or more of the compounds of formula (I) present in the composition have R's each positioned cis to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group. In yet another preferred embodimentAbout 90 mole% or more of the R's in the compound of formula (I) present in the composition having each R located in the cis position relative to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group. In another preferred embodiment, about 95 mole% or more (e.g., about 96 mole% or more, about 97 mole% or more, about 98 mole% or more, or about 99 mole% or more) of the compounds of formula (I) present in the composition have each R located cis to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety 1 、R 2 And R 3 A group.
The compounds of formula (I) may be prepared by using any suitable method or synthetic method. For example, the compounds may be prepared by first reacting the desired 4-alkylcyclohexylamine with 3, 5-dinitrobenzoyl chloride (3, 5-dichlorobenzoic acid chloride) to produce an intermediate compound of formula (A) below
(A)
The intermediate compound of formula (a) may then be reduced by using known methods (e.g., hydrogenation) to produce the corresponding diamine compound of formula (B) below
(B)
The compound of formula (B) may then be reacted with the desired 4-alkylcyclohexanecarbonyl chloride to produce the desired compound of formula (I). In this last step, a mixture of two different 4-alkylcyclohexanecarbonyl chlorides can be reacted with a compound of formula (B) to prepare compounds wherein R is 2 And R 3 Different (or in different spatial relationship with respect to the non-hydrogen substituent attached to the 1-position of the corresponding cyclohexanediyl moiety) compounds of formula (I). However, the reaction products prepared using mixtures of different 4-alkylcyclohexanecarbonyl chlorides may also compriseIn which R is 2 And R 3 The same compound of formula (I). Subsequent purification may therefore be necessary to separate the desired asymmetric compound from these other components.
Alternatively, to prepare asymmetric compounds of formula (I) (e.g., wherein R is 2 And R 3 Different compounds) 3-amino-5-nitrobenzoic acid can be reacted with the desired 4-alkylcyclohexanecarbonyl chloride to prepare intermediate compounds of the following formula (J)
(J)
The intermediate compound of formula (J) is then reacted with oxalyl chloride to produce the corresponding acid chloride of formula (K)
(K)
The acid chloride of formula (K) can then be reacted with the desired 4-alkylcyclohexylamine to prepare an intermediate compound of formula (L) below
(L)
The intermediate compound of formula (L) may then be hydrogenated by using known methods to prepare the corresponding amine compound of formula (M) below
(M)
Finally, the amine compound of formula (M) may be reacted with the desired 4-alkylcyclohexanecarbonyl chloride to produce the desired compound of formula (I).
In a second embodiment, the present invention provides a polymer composition comprising a compound of formula (I) and a polymer. In such embodiments, the compound of formula (I) may be any of the embodiments discussed above in connection with the first embodiment of the invention (e.g., a specific compound or composition comprising a mixture of compounds).
The polymer composition may comprise any suitable polymer. Preferably, the polymer is a thermoplastic polymer (e.g., polyolefin, polyester, polyamide, polylactic acid, polycarbonate, acrylic polymer) or a mixture thereof. More preferably, the polymer is a polyolefin polymer, such as a polypropylene polymer, a polyethylene polymer, a polymethylpentene polymer (e.g., poly (4-methyl-1-pentene)), a polybutene polymer, a poly (vinylcyclohexane) polymer, and mixtures thereof. In a preferred embodiment, the polymer is a polypropylene polymer. More preferably, the polymer is selected from the group consisting of polypropylene homopolymers (e.g., atactic polypropylene homopolymers, isotactic polypropylene homopolymers, and syndiotactic polypropylene homopolymers), polypropylene copolymers (e.g., polypropylene random copolymers), polypropylene impact copolymers, and mixtures thereof. Suitable polypropylene copolymers include, but are not limited to: random copolymers prepared from the polymerization of propylene in the presence of a comonomer selected from the group consisting of ethylene, but-1-ene (i.e., 1-butene) and hex-1-ene (i.e., 1-hexene). In the polypropylene random copolymer, the comonomer can be present in any suitable amount, but is typically present in an amount less than about 10 weight percent (e.g., about 1 to about 7 weight percent). Suitable polypropylene impact copolymers include, but are not limited to: those prepared by adding a copolymer selected from the group consisting of ethylene-propylene rubber (EPR), Ethylene Propylene Diene Monomer (EPDM), polyethylene and plastomer to polypropylene homopolymer or polypropylene random copolymer. In the polypropylene impact copolymer, the copolymer can be present in any suitable amount, but is typically present in an amount of about 5 to about 25 weight percent. In a preferred embodiment, the polymer composition comprises a polyolefin polymer selected from the group consisting of polypropylene homopolymers, polypropylene random copolymers, and mixtures thereof. More preferably, the polymer composition comprises a polypropylene random polymer.
The polymer compositions of the present invention may comprise any suitable amount of one or more of the compounds of formula (I) described above. In a preferred embodiment, the polymer composition comprises at least 0.001% by weight of compound of formula (I), relative to the total weight of the composition. In another preferred embodiment, the polymer composition comprises at least 0.002 wt. -%, at least 0.003 wt. -%, at least 0.004 wt. -%, at least 0.005 wt. -%, at least 0.01 wt. -%, at least 0.02 wt. -%, at least 0.03 wt. -%, at least 0.04 wt. -%, at least 0.05 wt. -%, at least 0.1 wt. -%, at least 0.3 wt. -%, at least 0.5 wt. -%, at least 1 wt. -%, at least 5 wt. -%, or at least 10 wt. -% of the compound of formula (I) relative to the total weight of the composition. In another embodiment, the polymer composition preferably comprises less than 99% by weight of the compound of formula (I), relative to the total weight of the composition. In another preferred embodiment, the polymer composition comprises less than 95 wt. -%, less than 80 wt. -%, less than 50 wt. -%, less than 25 wt. -%, less than 10 wt. -%, less than 5 wt. -%, less than 2 wt. -%, less than 1 wt. -%, less than 0.5 wt. -%, less than 0.2 wt. -%, less than 0.1 wt. -% or less than 0.07 wt. -% of the compound of formula (I) relative to the total weight of the composition. In a series of particularly preferred embodiments, the polymeric composition comprises from 0.001% to 0.5% (e.g., from 0.01% to 0.5% or from 0.05% to 0.5%), from 0.001% to 0.2% (e.g., from 0.01% to 0.2% or from 0.05% to 0.2%), from 0.001% to 0.1% (e.g., from 0.01% to 0.1% or from 0.05% to 0.1%) or from 0.001% to 0.07% (e.g., from 0.01% to 0.07%) by weight of the compound of formula (I), relative to the total weight of the composition. As mentioned above, the polymer composition of the invention may comprise more than one compound of formula (I). In those embodiments in which the polymer composition comprises more than one triamide compound of formula (I), each triamide compound can be present in an amount that falls within one of the above ranges, or the combined amount of all triamide compounds can fall within one of the above ranges.
The polymer compositions described herein may comprise other polymer additives in addition to one or more compounds of formula (I). Suitable additional polymer additives include, but are not limited to: antioxidants (e.g., phenolic antioxidants, phosphite antioxidants, and combinations thereof), antiblock agents (e.g., amorphous silica and diatomaceous earth), pigments (e.g., organic and inorganic pigments), and other colorants (e.g., dyes and polymeric colorants), fillers and reinforcing agents (e.g., glass fiber, talc, calcium carbonate, and magnesium oxysulfate whiskers), nucleating agents, clarifiers, acid scavengers (e.g., metal salts of fatty acids, such as stearic acid), polymer processing additives (e.g., fluoropolymer-containing polymer processing additives), polymer crosslinkers, slip agents (e.g., fatty acid amide compounds obtained from the reaction between a fatty acid and ammonia or an amine-containing compound), fatty acid ester compounds (e.g., fatty acid ester compounds obtained from the reaction of a fatty acid with a hydroxyl-containing compound, such as glycerol, sodium lauryl sulfate, and sodium lauryl sulfate), and combinations thereof, Fatty acid ester compounds obtained by reaction between diglycerol and combinations thereof), and combinations of the foregoing.
The polymer compositions described herein can be prepared by any suitable method. For example, the polyolefin composition can be prepared by simple mixing (e.g., high shear or high intensity mixing) of the polyolefin polymer, one or more compounds of formula (I), and any additional optional components. Alternatively, an additive composition comprising one or more compounds of formula (I) and any additional optional components (such as those described above) may be pre-mixed to provide a pre-mixed composition. This pre-mixed composition can then be mixed with a polymer to produce the polymer composition described above. The polymer composition may be provided in any manner suitable for further processing to prepare an article. For example, the polymer composition can be provided in the form of a powder (e.g., a free-flowing powder), a tablet, a pellet, a granule, a tablet, an agglomerate, and the like.
The polymer compositions described herein are believed to be useful in the preparation of thermoplastic articles. The polymer composition may be formed into the desired thermoplastic article by any suitable technique, such as: injection molding, injection rotational molding, blow molding (e.g., injection blow molding or injection stretch blow molding), extrusion (e.g., sheet extrusion, film extrusion, cast film extrusion, or foam extrusion), extrusion blow molding, thermoforming, rotational molding, film blowing (blown film), film casting (cast film), and the like.
The polymer compositions described herein may be used to produce any suitable article or product. Suitable products include, but are not limited to, medical devices (e.g., pre-filled syringes for retort applications, intravenous supply containers, and blood collection devices), food packaging, liquid containers (e.g., containers for beverages, pharmaceuticals, personal care compositions, shampoos, and the like), garment boxes, microwavable items, shelves, cabinet doors, machine parts, automotive parts, sheets, tubing, tubes, rotomolded parts, blow molded parts, films, fibers, and the like.
It has been observed that the polymer compositions of the present invention exhibit a very desirable combination of low haze combined with low leaching of the triamide compound of formula (I). Polymer compositions containing compounds of formula (I), such as polypropylene random copolymer compositions, typically exhibit haze levels that are at least 15% lower than the haze levels exhibited by polymer compositions containing structurally similar triamide compounds not covered by formula (I). In addition, it has been observed that polymer compositions containing certain compounds of formula (I) exhibit single digit haze levels that are comparable to those exhibited by more transparent polymers, such as polystyrene and acrylic polymers. As mentioned above, these polymer compositions also show excellent (i.e. low) leaching of the compound of formula (I) from the polymer composition. In fact, it has been observed that polymer compositions containing certain compounds of formula (I) exhibit leaching levels that are one to two orders of magnitude lower than those exhibited by polymer compositions containing structurally similar triamide compounds not covered by formula (I). It is believed that these properties exhibited by the polymer compositions of the present invention make the polymer compositions particularly well suited for use in the manufacture of thermoplastic articles or products requiring low haze levels and low leaching, such as articles and products intended for food contact and medical applications.
The following examples further illustrate the above subject matter but, of course, should not be construed as in any way limiting its scope.
Example A
This example illustrates the preparation of a triamide compound according to the invention.
6.5g (41.8mmol) of 50/50 mixture comprising 4-cis-tert-butylcyclohexylamine and 4-trans-tert-butylcyclohexylamine and a spoon tip (a tip of a spatula) of anhydrous LiCl were added to 200ml of tetrahydrofuran p.a. (THF) under an inert atmosphere. 3.3g (41.8mmol) of anhydrous pyridine were added and the solution was cooled to 5 ℃. Then, 8.8g (38.1mmol) of 3, 5-dinitrobenzoic acid chloride was added stepwise. The reaction mixture was stirred at 25 ℃ for 2 hours. Thereafter, the solvent was removed and the solid residue was stirred in about 500ml of water. After the water was decanted, the solid residue was dissolved in 50ml MeOH and precipitated in water. The precipitate was filtered off and dried.
11.7g (33.5mmol) of the precipitate obtained above were hydrogenated in a THF/MeOH mixture (200ml/50ml) with 1.0g Pd/C (10% by weight). The reactor was closed and purged 3 times with nitrogen and 3 times with hydrogen while stirring. The hydrogenation was carried out at 35 ℃ and 3 bar hydrogen pressure for 12 hours. The reaction mixture was transferred to a flask under an inert atmosphere and filtered through alumina (Alox N) to remove catalyst and water.
10.2g (35.2mmol) of the amine obtained above and a spoon of anhydrous LiCl were added to 350ml of tetrahydrofuran p.a. (THF) under an inert atmosphere. 5.5g (70.0mmol) of anhydrous pyridine were added and the solution was cooled to 5 ℃. Then, 14.2g (70.3mmol) of cis-4-tert-butylcyclohexylcarboxylic acid chloride was added. The reaction mixture was stirred at 25 ℃ for 2 hours. Thereafter, the solvent was removed and the solid residue was stirred in about 400ml of water for 15 minutes. After filtering the solid product, it was added to 1L N, N-Dimethylformamide (DMF) and boiled under reflux for 5 minutes. After cooling to room temperature, the residue is filtered off and dried in a vacuum oven.
Subsequent analysis of the product obtained confirmed that it was N- (4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butyl ] NCyclohexylcarbonylamino group]-benzamide. Of the product 1 H NMR confirmed that about 90 mol% of the product was N- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino]-benzamide.
Example B
This example illustrates the preparation of a triamide compound according to the invention.
Under an inert atmosphere, 4.3g (28.0mmol) of cis-4-tert-butylcyclohexylamine and a spoon-tipped anhydrous LiCl were added to 250ml of tetrahydrofuran p.a. (THF). 2.3g (28.5mmol) of anhydrous pyridine are added, 2.7g (25.0mmol) of trimethylchlorosilane are added and the solution is cooled to 5 ℃. Then, 5.8g (25.1mmol) of 3, 5-dinitrobenzoic acid chloride was added stepwise. The reaction mixture was stirred at 25 ℃ for 2 hours. Thereafter, the reaction mixture was added to 2 liters of ice water with vigorous stirring. After stirring for 2 hours, the precipitate was filtered off and dried in a vacuum oven at 40 ℃.
8.3g (24.0mmol) of the precipitate obtained above are hydrogenated in a THF/MeOH mixture (250ml/50ml) with 0.24g Pd/C (10% by weight). The reactor was closed and purged 3 times with nitrogen and 3 times with hydrogen while stirring. The hydrogenation was carried out at 35 ℃ and 5 bar hydrogen pressure for 12 hours. The reaction mixture was transferred to a flask under an inert atmosphere and filtered through alumina (Alox N) to remove catalyst and water.
6.4g (22.1mmol) of the amine obtained above and a spoon of anhydrous LiCl were added to 250ml of tetrahydrofuran p.a. (THF) under an inert atmosphere. 4.2g (53.3mmol) of anhydrous pyridine and 2.4g (22.0mmol) of trimethylchlorosilane are added and the solution is cooled to 5 ℃. Then, 8.3g (41.1mmol) of cis-4-tert-butylcyclohexylcarboxylic acid chloride and 1.1g (5.6mmol) of trans-4-tert-butylcyclohexylcarboxylic acid chloride were added. The reaction mixture was stirred at 25 ℃ for 2 hours. Thereafter, the reaction mixture was added to 2 liters of ice water with vigorous stirring. After stirring for 2 hours, the precipitate was filtered off and dried in a vacuum oven at 40 ℃.
Subsequent analysis of the product obtained confirmed that it was N- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino]-benzamide. Product produced by birthOf an object 1 H NMR confirmed that about 90 mol% of the product was N- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino]-benzamide.
Example C
This example describes the preparation of a triamide compound according to the invention.
Under an inert atmosphere, 4.3g (28.0mmol) of cis-4-tert-butylcyclohexylamine and a spoon-tipped anhydrous LiCl were added to 250ml of tetrahydrofuran p.a. (THF). 2.3g (28.5mmol) of anhydrous pyridine and 2.7g (25.0mmol) of trimethylchlorosilane are added and the solution is cooled to 5 ℃. Then, 5.8g (25.1mmol) of 3, 5-dinitrobenzoic acid chloride was added stepwise. The reaction mixture was stirred at 25 ℃ for 2 hours. Thereafter, the reaction mixture was added to 2 liters of ice water with vigorous stirring. After stirring for 2 hours, the precipitate was filtered off and dried in a vacuum oven at 40 ℃.
8.3g (24.0mmol) of the precipitate obtained above are hydrogenated in a THF/MeOH mixture (250ml/50ml) with 0.24g Pd/C (10% by weight). The reactor was closed and purged 3 times with nitrogen and 3 times with hydrogen while stirring. The hydrogenation was carried out at 35 ℃ and 5 bar hydrogen pressure for 12 hours. The reaction mixture was transferred to a flask under an inert atmosphere and filtered through alumina (Alox N) to remove catalyst and water.
6.4g (22.1mmol) of the amine obtained above and a spoon of anhydrous LiCl were added to 250ml of tetrahydrofuran p.a. (THF) under an inert atmosphere. 4.2g (53.3mmol) of anhydrous pyridine and 2.4g (22.0mmol) of trimethylchlorosilane are added and the solution is cooled to 5 ℃. Then, 9.4g (46.7mmol) of cis-4-tert-butylcyclohexylcarboxylic acid chloride was added. The reaction mixture was stirred at 25 ℃ for 2 hours. Thereafter, the reaction mixture was added to 2 liters of ice water with vigorous stirring. After stirring for 2 hours, the precipitate was filtered off and dried in a vacuum oven at 40 ℃.
The product obtained was N- (cis-4-tert-butylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide.
Example D
This example illustrates the preparation of a polymer composition according to the invention and the properties of such a polymer composition.
The powdered propylene random copolymer (SA 849 RCP from LyondellBasell) was mixed intensively with the appropriate amount of the corresponding triamide compound (sample a from example a and sample B from example B) to obtain a masterbatch containing 2 wt% of the triamide compound. The resulting masterbatch was mixed with a suitable amount of neat polymer to obtain a polymer composition containing 0.08 wt% of the triamide compound.
The formulations were compounded on a co-rotating laboratory twin screw extruder at a screw speed of 100rpm and a temperature of about 240 ℃ for about 5 minutes. About 5.0g of the melt was transferred directly into the barrel of a DSM Xplore 12ml (RTM) microinjector and injected into the polished mold at a pressure of about 6 bar and a temperature of about 240 ℃. The resulting sample had a diameter of 2.5 cm and a thickness of about 1.1mm and was used for further optical characterization (% haze). The results of these haze measurements are listed in table 1 below.
TABLE 1
As can be seen from the data in table 1, the polymer compositions containing the triamide compounds according to the present invention (i.e., samples a and B) exhibited significantly reduced haze compared to the control. These data indicate that the triamide compounds of the present invention are effective clarifying agents for polymers such as polypropylene.
Example E
This example illustrates the synthesis of the triamide compounds of the present invention (i.e., the triamide compounds of formula (I)).
N- (cis-4-tert-pentylcyclohexyl) -3, 5-dinitrobenzamide was synthesized by adding 36.07g of 3, 5-dinitrobenzoyl chloride to 400mL of anhydrous THF and 15mL of pyridine. The reaction mixture was stirred for 5 minutes and cooled to 20 ℃ in an ice-water bath. Cis-4-tert-amylcyclohexylamine (28.61g), dissolved in 100ml of anhydrous THF, was then added dropwise over a half hour period at a rate which allowed the reaction temperature to rise to 30 ℃. The reaction mixture was stirred overnight and then 300mL of MeOH was added. The THF was largely removed by rotary evaporation and the remaining methanol solution was added dropwise to 3L of DI water with vigorous stirring. The fine yellow precipitate was isolated by filtration, slurried twice with water (1L, 20 min), collected by filtration after each wash, and then slurried twice with diethyl ether (800mL, 15 min). The collected solids were air-dried and then dried in a vacuum oven at 60 ℃ for 17 hours to give a pale yellow powder.
2000mL of Parr Reactor (Model 4522M) were purged with nitrogen, and then 1.02g of 10 wt% palladium on carbon were charged. Subsequently, 1L THF was added to the reactor. Then, 14.00g of the N- (cis-4-tert-pentylcyclohexyl) -3, 5-dinitrobenzamide obtained above was dissolved in 600mL of THF and charged into the reactor. The reactor was sealed and purged with nitrogen (4x 60psi) and then heated to 40 ℃ with stirring at 1800 rpm. After 15 minutes of equilibration, the reactor was purged with hydrogen (5x 70psi), then pressurized to 100psi with hydrogen and held at temperature with stirring for 19 hours. The reaction material was filtered to remove the catalyst and the solvent was removed by rotary evaporation to give a glassy material with a pale red color. This reaction produces 3, 5-diamino-N- (cis-4-tert-amylcyclohexyl) benzamide.
11.79g (38.69mmol) of the 3, 5-diamino-N- (cis-4-tert-amylcyclohexyl) benzamide obtained above were added to 800mL of anhydrous Tetrahydrofuran (THF) under an inert atmosphere. 7.5mL of anhydrous pyridine were added and the reaction mixture was cooled to 15 ℃ with the aid of an ice-water bath. Then, 17.26g (85.1mmol) of cis-4-tert-butylcyclohexanecarboxylic acid chloride was added. The reaction mixture was stirred at 15 ℃ for 0.5 hour and at 21 ℃ for 21 hours. About 800mL was removed by rotary evaporation, and then 500mL of methanol was put into the reaction slurry and stirred for 15 minutes. The reaction slurry was then added to a beaker containing 2500mL of Deionized (DI) water with stirring. After complete addition of the slurry, the system was stirred for 10 minutes and the product was collected by suction filtration. The solid was then slurried in 2000mL of 75/25DI water/methanol mixture for 1 hour, and the solid was collected by suction filtration. The crude product was reslurried in 300mL of diethyl ether for 30 minutes and collected by suction filtration. The product solid was dried in a vacuum oven at 105 ℃ for 19 hours. The product obtained was N- (cis-4-tert-amylcyclohexyl) -3, 5-bis- [ cis-4-tert-butylcyclohexylcarbonylamino ] -benzamide.
Example F
This example illustrates the preparation of a polymer composition according to the invention and the properties of such a polymer composition.
Seventeen triamide compounds were first synthesized according to the general procedure described above and demonstrated in examples a through C and E. The triamide compounds are listed in table 2 below. For simple comparison of the various compounds, the triamide compounds all have a similar cis content.
Table 2 compound ID and compound name of the triamide compound used to prepare the polymer compositions.
The polymer compositions were prepared by compounding each of the triamide compounds into a 12MFR polypropylene random copolymer (SA 849 RCP from LyondellBasell). The triamide compounds (i.e., compounds 1 through 17) were each gravimetrically added to polymer pellets (0.80 grams of powder additive per 1000 grams of additive/polymer mixture to obtain 800ppm triamide compound), which were then mixed in a Henschel high intensity mixer. The resulting mixture was melt compounded at 240 ℃ on a Deltaplast single screw compounding extruder with a screw diameter of 25mm and a length to diameter ratio of 30: 1. The extrudate (in the form of a strand) of each sample was cooled in a water bath and then pelletized. The melt compounded polymer composition was then injection molded by using a 40 ton ARBURG ALLROUNDER 221K injection molding machine at 240 ℃ flat profile barrel temperature (flat profile barrel temperature) and 100 bar back pressure to prepare a sheet (platque) having dimensions of about 51mm x 76mm and a thickness of 0.76 mm. After aging for 24 hours, the dimensions of the panels were verified with a micrometer.
The percent Haze of the plaques (including control plaques made without the triamide compound) were then measured using BYK-Gardner Haze-Guard Plus according to ASTM standard D1103-92.
The plates were also tested to determine the amount of triamide compound leached using a set of specified conditions. In particular, the leaching was performed at 100 ℃ for 2 hours using a 550mL stainless steel vessel with a stainless steel lid with a teflon liner. A glass spacer was used to ensure separation of the polymer sample during the migration test. The leaching uses 25% ethanol solution. Ethanol is absolute grade. The water is deionized with an ion exchange purification system to obtain deionized water. Repeated migration tests in solvent were performed using two plates immersed in 250mL of solvent. A control plate without the triamide compound was also prepared and leached using the above conditions. An aliquot (-1 mL) was removed from the leaching solvent after each heating time and added to a vial for LC analysis.
A 1000ppm solution of each triamide compound was prepared by dissolving 0.100g of the triamide compound in NMP, and a dilution was prepared in 100% ethanol. These solutions were used to obtain a calibration curve for each triamide compound. Water ACQUITY UPLC with Phenomenex Kinetex (particle size 2.6 μm) as analytical column and PDA and MS as detector was used as LC device. The column temperature was 40 ℃. The mobile phases used were methanol and water. The flow rate was set to 0.4 mL/min. The amount of sample is 1 to 5. mu.L. The mass spectrometer was used in Single Ion Recording (SIR) mode with SQD2 detector. The wavelength in the PDA detector was set to 200 to 800 nm. Each triamide compound was identified by comparing its retention time to the corresponding peak in the standard solution and its MS and UV spectra. Quantification was performed using an external standard calibration curve. The limit of detection (LOD) is determined by extrapolation to a 3:1 signal-to-noise ratio.
The results of the haze and leaching measurements are listed in table 3 below. In the column of leached amounts, the symbol "n.d." means "not detected", meaning that the amount of leached triamide compound, if any, cannot be quantified, since the measurement does not return a signal that exceeds the above detection Limit (LOD).
Table 3 leaching and haze measurements of polymer compositions prepared with compounds 1 through 17 and control polymer compositions.
As can be seen from the data in Table 3, with R therein 1 、R 2 And R 3 The polymer compositions prepared from triamide compounds of formula (I) that are alkyl groups (i.e., the polymer compositions prepared with compounds 2 through 10, 12 through 14, and 16 through 17) each exhibit a haze level that is significantly lower than that exhibited by R wherein R 1 、R 2 Or R 3 Compounds in which at least one of (a) is non-alkyl (i.e., compounds 1, 11, and 15) exhibit haze levels. When R of the triamide compound is 1 、R 2 And R 3 The difference in haze levels is even more pronounced when the group is an alkyl group having three or more carbon atoms. Furthermore, when the triamide compound has a branched alkyl group, especially when at least R 2 And R 3 With branched alkyl groups, the difference in haze levels is greater.
With respect to leaching, the triamide compounds of the present invention generally exhibit a ratio of R to R, wherein R 1 、R 2 And R 3 A similar triamide compound which is a hydrogen atom is less leached. The level of leaching generally decreases with increasing number of carbon atoms in the alkyl group. Presence of branched alkyl groups, especially when at least R 2 And R 3 Branched alkyl groups also reduce the level of leaching.
In view of the above, the inventors believe that the triamide compounds of the present invention are distinguished by their highly desirable combination of low haze and low leaching. It is believed that polymer compositions made with such triamide compounds are suitable for use in a wide range of applications (e.g., food contact and medical device applications) where it is desirable for the polymer composition to exhibit low haze and leaching levels.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms "a" and "an" and "the" and similar referents in the context of describing the subject matter of the present application (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as" or "such as") provided herein, is intended merely to better illuminate the subject matter of the application and does not pose a limitation on the scope of the subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the subject matter described herein.
Preferred embodiments of the subject matter of the present application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the subject matter described herein to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.
Claims (19)
1. A compound of formula (I)
(I)
Wherein R is 1 、R 2 And R 3 Independently selected from alkyl groups.
2. The compound of claim 1, wherein R 1 、R 2 And R 3 Is independently selected from C 1 -C 8 An alkyl group.
3. A compound according to claim 1 or claim 2, wherein R is 1 、R 2 And R 3 At least one of which is a branched alkyl group.
4. The compound of claim 3, wherein R 1 、R 2 And R 3 At least two of which are branched alkyl groups.
5. The compound of claim 4, wherein R 2 And R 3 Is a branched alkyl group.
6. The compound of claim 4, wherein R 1 、R 2 And R 3 Each of which is a branched alkyl group.
7. The compound of claim 1, wherein the compound is selected from the group consisting of:
n- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-isopropylcyclohexylcarbonylamino ] -benzamide;
n- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
n- (4-N-propylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
n- (4-N-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-isopropylcyclohexylcarbonylamino ] -benzamide;
n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
n- (4-tert-pentylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide;
n- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide;
n- (4-tert-amylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide;
and mixtures thereof.
8. The compound of claim 6, wherein said compound is N- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide.
9. The compound of claim 6, wherein said compound is N- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-tert-amylcyclohexylcarbonylamino ] -benzamide.
10. The compound of claim 6, wherein said compound is N- (4-tert-amylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide.
11. The compound of claim 6, wherein said compound is N- (4-N-propylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide.
12. The compound of claim 6, wherein said compound is N- (4-N-butylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide.
13. The compound of claim 6, wherein said compound is N- (4-isopropylcyclohexyl) -3, 5-bis- [ 4-tert-butylcyclohexylcarbonylamino ] -benzamide.
14. The compound of claim 6, wherein said compound is N- (4-tert-butylcyclohexyl) -3, 5-bis- [ 4-isopropylcyclohexylcarbonylamino ] -benzamide.
15. A polymer composition comprising:
(a) a compound according to any one of claims 1 to 14; and
(b) a polyolefin polymer.
16. The polymer composition of claim 15, wherein the polyolefin polymer is a polypropylene polymer.
17. The polymer composition of claim 16, wherein the polyolefin polymer is selected from the group consisting of polypropylene homopolymers, polypropylene random copolymers, and mixtures thereof.
18. The polymer composition of claim 17, wherein the polyolefin polymer is a polypropylene random copolymer.
19. The polymer composition of any of claims 15-18, wherein the compound of formula (I) is present in the composition in an amount of about 0.001 wt.% or more based on the total weight of the polymer composition.
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| WO2010069854A2 (en) * | 2008-12-19 | 2010-06-24 | Basf Se | Modified polyolefin waxes |
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| CA2436960C (en) | 2000-12-06 | 2012-08-07 | Ciba Specialty Chemicals Holding Inc. | Polypropylene resin compositions |
| MXPA04011840A (en) | 2002-05-30 | 2005-03-31 | Ciba Sc Holding Ag | ß CRYSTALINE POLYPROPYLENES. |
| WO2004072168A2 (en) * | 2003-02-14 | 2004-08-26 | Ciba Specialty Chemicals Holding Inc. | Resin compositions |
| CN1867540B (en) | 2003-10-17 | 2010-05-26 | 新日本理化株式会社 | Amides, polyolefin resin compositions, and moldings |
| KR101154564B1 (en) | 2003-12-26 | 2012-06-08 | 신닛폰 리카 가부시키가이샤 | Method and composition for control of crystallization rate of polyolefin resin, resin composition and resin molding |
| CN101568585B (en) | 2006-12-19 | 2011-08-10 | 新日本理化株式会社 | Novel polyolefin resin composition and molded resin obtained therefrom |
| JP2010070621A (en) | 2008-09-17 | 2010-04-02 | New Japan Chem Co Ltd | Masterbatch and method for manufacturing the same |
| US9029446B2 (en) | 2009-12-07 | 2015-05-12 | Basf Se | Clarified polypropylene articles with improved optical properties and/or increased temperature of crystallization |
| JP5794096B2 (en) * | 2011-10-18 | 2015-10-14 | コニカミノルタ株式会社 | Optical film, polarizing plate, and liquid crystal display device |
| US20150114257A1 (en) * | 2012-05-01 | 2015-04-30 | Konica Minolta, Inc. | Method of preparing retardation film, polarizing plate, and liquid crystal display |
| EP3037466A1 (en) | 2014-12-23 | 2016-06-29 | Dow Global Technologies LLC | Polyethylene compositions with improved optical properties |
| BR112018015160B1 (en) | 2016-03-09 | 2022-07-19 | Milliken & Company | TRISAMIDE COMPOUNDS AND COMPOSITIONS COMPRISING THE SAME |
| KR20220114022A (en) | 2019-12-12 | 2022-08-17 | 밀리켄 앤드 캄파니 | Trisamide compound and composition comprising same |
| US11667603B2 (en) | 2019-12-12 | 2023-06-06 | Milliken & Company | Trisamide compounds and compositions comprising the same |
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| US20080249269A1 (en) * | 2007-04-05 | 2008-10-09 | Hui Chin | Electret materials |
| WO2008122525A1 (en) * | 2007-04-05 | 2008-10-16 | Basf Se | Electret materials |
| WO2010069854A2 (en) * | 2008-12-19 | 2010-06-24 | Basf Se | Modified polyolefin waxes |
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